Production and use of anthracene dyes



Patented Sept. 11, 1934 PRODUCTION AND USE OF ANTHRACENE DYES Robert Fraser Thomson, Ian ,Blohin Anderson, and Sidney Thornley, Grangemouth, Scotland, assignors to Imperial Chemical Industries Limited a corporation of Great Britain No Drawing. ApplicationAugust19.1931 Serial, I No. 558 186. In Great Britain August 25,. 1930 14 Claims. (Cl. 260-61) This invention relates to the production and use of benzanthrone derivatives; more particu-.- larly it relates to the manufacture of bodies having a benzanthrone nucleus and containing se- 5 lemum, and to their use a's'intermediates in the production of further products and coloring maters, some of which do not contain selenium.

It is ail-object of this invention to'provide a new series of intermediates of the benzanthrone series containing selenium. It is a furthertob-' ject of the invention to provide new processes for the production of further intermediates and coloring matters, using their selenium-containing intermediates as starting materials. It is a '15. further object of the invention to provide a new process for the manufacture of dibenzanthrones and isodibenzanthrones. Other objects will appear hereinafter, 1 I

,These objects are accomplished as set out in the following specification, and claims.

.We have found that selenium and selenium compounds react. readily with l benzanthrone bodies to give what may be called primary prod-.

uc'tsi containing selenium. These primary prodi ucts yield further valuable products, which are herein referred to as"secondary products, when submitted to various chemical treatments such asitreatment with acid or alkaline condensing agents, nitration, halogenation, sulphonation, oxidation, reduction of condensation with organic halogen compounds. Both the primary and the secondary products can be used in some cases as intermediates and in some cases as color'ing matters, e. g. vat dyes,cor as both.

As starting materials for the primary products we use benzanthrones, including bromo-, chloro-, methyl-, nitro-, ethoxyand similarly substituted benzanthrones and we treat these starting materials with the element selenium or with reactive compounds thereof such as selenium dioxide or selenious acid.

The treatment may be carried out;in the presence or absence of solvents or diluents with; or without addition of assisting substances such a '5 acid absorbers or catalysts. l

The resulting primary products are then treated for conversion into the secondary products by the methods already outlined and these secondary products may further be converted into other products in certain cases.

Primary products of the benzanthrone series may'be obtained by treating benzanthronesor their derivatives with selenium or selenium' com pounds either alone' or in the presence of *organic or inorganic solvents or diluents with or without acid absorbers or catalysts. The resulh ing products appearv tolbe analogousto certain known sulphur derivatives of benzanthrone such.

as benzanthrone sulphide. dibenzanthronyl sulphide, benzanthrone mercaptans, benzanthrone 9; sulphones, etc. and it is possible that. they cansist. of the corresponding selenium compounds. For example, treatment of fizl-chlorobenzan-q throne with selenium and caustic. soda new body is obtained which appears to be Bzl-dibenzam Q thronyl hydrogen selenide oi formula i and on treatment of Bzl-chlorobenzanthrone with, selenium powderv and sodium acetate in tetra-hydronaphthalene a product which appea s to be the corresponding BzlrBzl' dibenzanthronyl selenide'is obtained. Ontreatment of this latter body with hydrogen peroxidei'n concentrated sulphuric acid an oxidation product is obtained which may be a 'dib'enzanthronyl selenone of the formula Corresponding bodies, which contain chloromethyl, nitro, and other substituents can also be obtained.- In general the processes give excellent yields I of productsiin some cases equal to those the-.- oreticallyf possible. The products are also in manypases readily obtained in very pure form withoutfa specificpurification treatment. Fur ther in many cases the amount 01' selenium required; is only small and the results are surs prisingly' economical in] spite of the fact that selenium and its compounds arelrelatively rather expensive substances for purposes such'as the manufacture of dyestufis. One particular advantage of the process is the fact that it enables isodibenzanthrones and chlorinated idodibenzanthrones to-be readily obtained in excellentyields and of great purity. Halogenated' isodibenzanthrones which give dyeings of particular purity can be obtained by our process.

Our invention will best be understood from the following illustrative examples, but it is not to be regarded as in any way limited to these specific examples. The parts are parts by weight.

Example 1 parts of 97 per cent sulphuri'c'acid an'diIO'parts of finely divided selenium dioxide sprinkled in. The temperature is raised to,1 00 C. and kept at this for 24;.hours. changes from bright red to pale olive brown.

on dilution gives a violet blue suspension. The

' product obtained resembles isodibenzanthrone of selenium dioxide is substituted for selenium.

During heating. the colour'j After cooling the producti's boiled up with water and filtered. The brown residue remaining is boiled up again with the addition of a little alkali to the water, and again filtered; washed-with" water and dried. The dry product, on, extracting with 6 parts of nitrobenzene and cooling isobtained in the form ofreddish brown crystals. These dissolve'in sulphuric acid'to give a greenis h-blue solution. M I r Example 2 ,5 parts of the-product ofExample 1 are added to. av mixture of 50flparts of caustic potash and 30-p'artsofmethylated spirits, heated to 140 C; and kept at this for. 4 hours. The melt is then cooled, drowned in :water, boiled, air-blown and filtered. The .resultingdyestuff, which is apparently obtained in practically quantitative yield, dissolves in sulphuric acid with a green colour which becomes violet-blue on dilution with water. It dissolves in alkaline hydrosulphite giving a blue vat with a. reddish-brown fluorescence from which cotton is dyed in blue shades which on oxidizing becomes slightly violet.

p a rts offdyestuff obtained in Example 2 are dissolved in=20 parts of nitrobenizene with a little iodineand 2' parts of sulphuryl chloride added. The temperature is raised to C. and kept :at

this until no more hydrochloric acid is evolved.

The melt, which was at first green, becomes redviolet. 'iliiltrationfis carried-out at 7,0? (land the product'washed with nitrobenzene and alcohol. It forms a violet-red powder dissolving with a green colour in sulphuric acid, the green colour changing to violet-blue on dilution with water. With alkaline hydrosulphite it gives a greenishblue vat Without fluorescence from which cotton is dyed in slightly; greenish shades of blue, which becomes violet-blue on oxidizing. It dissolves in hot nitrobenaene giving a reddish-violet so- .lution with a brilliant-red-violet fluorescence.

J x p e 4' 5.29 parts of Bzl-chlorobenzanthrone areadded to 40parts oftetrahydronaphthalen'e containing 1.2 .parts of; grey seleniumpowde'r and 3 parts of sodium acetate. The' mixture is heatedzto the "boil under reflux for several. hours during which the colour changes from greenish-yellow to brown,and the'meltfiltered hot-.: The yield consists of about 4 parts of a yellowish-brown productiwhich dis'solvesinsulphuric acid with a bright greenishebluecolour and which maybe Bzl:Bzldibenzanthronyl selenide.'-

.- The produc'tof Example-4 is fused :with alcoholic potash using the .method described in Example2f... A bright blue meltis obtained, which I The product obtained is similar to that of Ex- 10 parts of benzanthrone are dissolved in 200 ample 4 and on fusion gives a good yield of dyestufi-'w'hich appears to be pure isodibenzan- I 9 parts of Bzl-chlorobenzanthrone, 50 parts of methylated spirit, 3 .parts of calcium hydroxide powder and Z-parts of selenium are mixed and heated in a closed vessel slowly to 180 C. and about 300 lbs. per square inch pressure. The temperature is maintained until conversion appears to be complete. I The melt is then cooled and the product filtered oil. On removal of excess selenium and calcium salts, what is apparently practically pure 'Bzl:B zl'-dibenzanthronyl selenide melting above 810 is obtained.

In this process catalysts likecopperinay be used and acid absorbers like quick lime, barium hydroxide, sodium phosphate,- sodium j acetate, may be used instead of calcium hydroxide. Tem- 'peratures' from 120 upwards are sufficient. to

effect conversion. Example 8 "If Example 7 is repeated using 3 parts of calcium hydroxide and 7 parts of sodium acetate a violet melt isobtained. f Inboiling up this melt with 400 parts Water and 30 parts of sodium selenide and filtering, a greenish yellow residue is left in the filter which "on working upjas before is found to be Bzl'zBzl' dibenzanthronyl'selenide. By carefully acidifyingthe' violet-filtrates a brilliant orange yellow product is precipitated which contains 25 per cent selenium and appears to be benzanthrone-Bzl hydrogen selenide. This body is not solubleiin caustic soda solution but dissolves readily in sodium sulphide or sodium selenide solutions. I, It

dissolves in concentrated sulphuric acid to give'a blue violet solution, and on melting at tempera-- turesofabout 300? C. is converted into a product containing BzlzBzP-diben'zanthronyl selenide.

' Example '9 7 Dry chlorine gas is passed intoa stirred mixture of 10 parts of dibenzanthronyl selenide, 100 parts of nitrobenzene and a trace of iodine for 8 hours,-

the temperature being maintainedat 18-20 C.

: -The solid is separated by filtration and' washed with nitrobenzen'e. The adhering nitrobenzene is removedby steam distillation and the product separated .by filtration and dried. The crude product contains 7.44 percent chlorine.

i of water, stirred, filtered, washed with cold Example 11 This is an examplecof the alkali fusion of the tetrabrom-derivative obtained inExampleBJ 70 parts of caustic potash and 48 partsof methylated spirits are mixed and heated to 120 C. stirring being commenced as soon as possible. At 120 C. parts of the tetrabrom body are added, the temperature raised to 130 C. and the whole kept at 130 C. for 6 hours. The mixture after cooling is extracted with 1000 parts of waterand air blown through for 60 minutes to oxidize. 200 parts of sodium sulphite are added and the whole'heated 'to boiling withfstirring. After cooling the mixture is filtered, washed with cold water until free from alkali and dried. Analysis showed that the bromine has been practically all removed. The product dyes cotton from the vat in a shade similar to that given by i'sodibenzanthrone.

Ex m This is an example of the oxidation of 'dibenzanthronyl selenide. 10 parts are dissolved by stirring in 150 partsof pure concentratedsulphuric acid at 17-20 C. While maintaining the temperature at17-20" Cl 15 parts of per cent hydrogen peroxide are added in 75 minutes and afterwards the whole stirred at 1720 C. for 65 minutes. The mixture is poured into 1500 parts ter until free from acid and dried.

Example 13 This-is an example of the alcoholic caustic potash fusion of the oxidation product of Example 12. parts of caustic potash are dissolved by stirring at 95-98 C. in 74 parts of methylated spirits, 5 parts of the oxidation product are added and the whole stirred at 95-98 C.'for minutes. The mixture is poured into 500 parts of water and a stream of air blown through for 30 minutes to oxidize. 50 parts of sodium sulphite are now added and the whole heated with stirring'to the boiling point. After cooling the productis filtered, washed with cold water 1mtil free from alkali and dried. i j

, It dyes cotton a shade similar to that given by isodibenzanthrone.

' Example 14 This is an example of the nitration of dibenzanthronyl selenide. 10 parts of the selenide and 75.2 parts of 96 per cent nitric acidare' stirred at room temperature overnight. The product is poured intQlOOO-parts of water, fi1tered,'washed with cold water until free from acid and dried.

When crystallized from nitrobenzene a small quantity of material is obtained which possesses a nitrogen content similar to that required for a tetranitro-derivative.

' I Example '15 This is an example of'the treatment of dibenzanthronyl selenide with 68 per cent nitric acid in the presence of concentrated sulphuric acid. 10 parts of the selenide are dissolved by stirring in 150 parts of pure concentrated sulphuric acid at 17-20 C. While maintaining the temperature at 17-20 C. 5 parts of 68 per cent nitric acid dissolved in 15 parts of pure concentrated sulphuric acid are added in 60 minutes. After wards the whole is stirred at 1-'720 C. for minutes. The mixture is poured into 1500 parts of water, stirred, filtered, washed with cold water until free from acid and dried. The crude product is crystallized from nitro-benzene.

WEL

Example 16 This is an example of the alcoholic caustic pot- 50 ash fusion of the product of Example 15. parts'of caustic potash are dissolved by stirring at'95-98 Chin 74 parts of methylated spirits. I. 5 parts of the product of Example l5are added and the whole-stirred at -98" C. for 60 minutes. The mixture is 'poured into 500 parts of water anda stream of air blown through for 30 minutes to oxidize. 50 parts of sodium sulphide are now added and the whole heated with stirring to the boiling point. After-cooling the product is'filtered, washed with cold water until free from alkali and dried.

It dyes cotton in grey shades from an alkaline hydrosulphite vat. r Example 17 This is an example of the production of a body whichappears to be Bzl-benzanthronyl hydrogen selenide.

20 parts of Bzl-chlorobenzanthrone, 80 parts of caustic soda, 80 parts of selenium, parts of water and 100 parts of methylated spirit are mixed together and refluxed for 24 hours. The resulting violet melt is then diluted with 1000 parts of water and filtered, The violetbrown paste is washed with a little Water, extracted with sodium sulphide solution to remove excess selenium and finally treated with dilute hydrochloric acid. The residue on drying is an orange yellow powder which is almost completely soluble in sodium sulphide solution giving a violet solution. It is insoluble in dilute caustic soda but dis:- solvesin concentrated sulphuric acid with a blue violet colour. It melts at 290-300 C. whena chemical change appears to take place. It contains 25 per cent selenium and appears to be Bzlb-enzanthronyl hydrogen selenide. When dimethyl sulphate is stirred in the cold into the sodium sulphide solution of the product obtained in this example a product which is probably Bzl-benzanthronyl methyl selenide is ob; tained. This orange yellow product gives a pure green-blue solution in sulphuric acid.

7 Example 18 iodine, a. product is obtained by filtering the cooled melt whichis insoluble in sodium sulphide and gives a. bright blue solution in sulphuric acid. This product consisting of an orange brown pow-- der and which is probably benzanthrone-B zlphenylselenide, on treatment in concentratedale coholic potash at 160 gives a very good yield of isodibenzanthroneof excellent purity.

Example 19 This is another example for the production'of the bodywhich appears to be BzlzBzli-dibng zanthronyl selenide.

1 part of benzanthrone-Bzl-hydrogen selenide is refluxed with 1 part of copper powder and 10 parts of nitrobenzene for several hours,'on' filtering the hot melt and cooling the fiitra'tes'wha't is apparently practically pure BzliBzl diben- Example 21 This is a further example of the production of the body which appears to be Bzl:Bzl'-dibenzanthronyl selenide.

1 part of Bzl-benzanthronyl hydrogen selenide is heated in a closed vessel with 10 parts of alcohol with a trace of copperand part of lime when a practically quantitative yield is obtained of the product described in Example 19.

Example 22 This is a further example of the production of the body which appears to be BzlzBzY-dibenzanthronyl selenide. I

' 5 parts of Bzl-benzanthronyl hydrogen selenide are refluxed with 5 parts of selenious acid in 50 parts of hitrobenzene.v On filtering the cooled melt a residue is obtained consisting of a mixture of a brown'powder, free selenium and selenious acid. This powder gives a bluish red solution in sulphuric acid which on being reprecipitated by water is found to be a mixture of the original material and Bzl:Bzl'-dibenzanthronyl selenide. The filtrates on steam distillation or dilution with methylated spirits yield a brown product which is practically insoluble in sodium sulphide solution and gives a dull violet blue solution in sulphuric acid. This body on refluxing in nitrobenze ne with copper powder is converted to Bzl :Bzl' -dibenzanthronyl selenide.

Example 23 This is a furth r example of the production of what appears to be Bzl:Bzl'-dibenzanthronyl selenide.

1 part of Bzl-benzanthronyl hydrogen selenide is dissolved in 10 parts of' sulphuric acid and stirred for 5 hours when the violet colour changes to red with evolution of a little sulphur dioxide. On precipitation by dilution with water an orange yellow body is thrown out which in extraction with sodium sulphide solution is found'to be mixture of the original starting material and some Bzl:Bzl-dibenzanthronyl selenide.

If the above is repeated at 50 C. the same process takes place. If carried out at C. the

colour of the solutionchanges through redto 50 parts of aluminium chloride are carefully dissolved in 200 parts of pure pyridine, 10 parts of BzlzBzl-dibenzanthronyl selenide are then stirred in and the mixture is refluxed for 24 hours. The dark red melt is cooled and. drowned in hydrochloric acid and the insoluble matter is filtered off and washed free of acid and aluminium salts.

The product which consists of a black violet powder contains what appears to'be isodibenzanthrone. It dissolves in sulphuric acid to 'givea dull blue green solution from which red violet flocks are precipitated on dilution and dyes cot- 8.5 ton red violetshades from a cornflower blue vat with red brown fluorescence.

On extraction with nitrobenzene practically pure isodibenzanthrone remains undissolved. The yield approaches the theoretical.

Example 25 dissolves in sulphuric acid to give a royal blue solution which on dilution gives red brown flocks.

Example 26 which when freed from excess selenium and 1-20 calcium salts appears to be a chlorinated dibenzanthronyl selenide of melting point about 290 C. The product gives a gree'n-bluesolution in sulphuric acid and an alcoholic potash fusion at temperatures above 100 C. gives a dyestuff of the isodibenzanthrone type in' good yield and of good purity. Example 27 This is an example of the production of what appears to be a diamino-Bzl:Bzl'-dibenzanthronyl selenide.

Ifthe previous example is repeated usingnitro- Bzl-chlorobenzanthrone (prepared according to Example 1 of B. P. 256,281) instead of the diohlorobenzanthrone, a product is obtained in excellent yield which appears to be an amino derivative, probably diamino e BzlzBzl' dibenzanthronyl'selenide. The product which is a red brown powder dissolved in sulphuric acid to give 1 a dark bluish green solution. On dilution yellow brown flocks are precipitated'which on treatment with alkali change to red brown. The product melts at 292-295" C. and on alcoholic potash fusion gives a dyestuif of the isodibenzanthrone type in good yield.

Example 28 p This is an example of the production of a body which also appears to belong to the Bz1:Bzl-dibenzanthronyl selenide type.

If the previous example is repeated using methoxy-Bzl-chlorobenzanthrone (prepared according to Example 4 of B. P. 256,281) a product is obtained in excellent yield which gives a bright grass green solution in sulphuric acid, melts about 265270 C., and on fusion with alcoholic potash gives a dyestufi of the isodibenzanthrone type in good yield and purity.

Example 29 5 parts of Bzl-chlorobenzanthrone, 50 parts of tetraline, 1.2 parts of selenium, 0.5 part of copper powder and 4 parts of sodium acetate are refluxed for several hours. On cooling, filtering ofi the insoluble matter and removing sodium salts etc., the body is obtained in practically pure form and in good yield. The same product is obtained if selenious acid is substituted for selenium.

Example 30 This is an example of the sulphonation of the product obtained in Example 7.

23.45 parts of the product obtained in Example 7 are added to 258.5 parts of 6.5 per cent oleum during 30 minutes, the temperature being maintained at 2225 C. The whole is now stirred at 22-25 C. until complete sulphonation has occurred as indicated by the complete solubility of a test portion in hot water. Afterwards the mixture is poured into 2500 parts of stirred cold water, 300 parts of salt added and the whole stirred overnight. It is filtered, the residue washed with 20 per cent salt solution until free from acid and dried.

Example 31 This is an example of the treatment of the product of Example 7 with 96 per cent nitric acid using nitrobenzene as solvent.

10 parts of the product of Example 7 are added to 100 parts of nitrobenzene and the whole stirred for 10 minutes. 30 parts of 96 per cent nitric acid are added, the temperature being allowed to rise to 35 C. The temperature is afterwards raised to 50 C. for 1 hour 20 minutes. Subsequently it is allowed to cool to room temperature and stirred at room temperature overnight. The whole is poured into 480 parts of methylated spirits,

stirred, the precipitated solid separated by filtracondensing agent until reaction is effected and a dyestufi is formed, the said condensing agent being a metal halide condensing agent of the class comprising aluminum chloride.

3. Unsymmetrical benzanthronyl having the general formula R1-SeR2 wherein R1 represents a benzanthronyl radical and R2 represents hydrogen or a metallic atom, or an alkyl or aryl radical, said benzanthronyl selenides being suitable for the preparation of intermediates and dyes.

4. Bzl-benzanthronyl hydrogen selenide.

5. Bzl:Bzl-dibenzanthronyl selenone.

6. The process of preparing a selenium derivative of benzanthrone, which comprises reacting benzanthrone with selenium dioxide in a medium of sulfuric acid.

7. The process of preparing a compound of the dibenzanthronyl-selenide series which comprises reacting a Bzl-halogen-benzanthrone with selenium dioxide in an organic solvent in the presence of an acid absorbing agent.

8. In the process of preparing a compound of the dibenzanthronyl selenide series, the step which comprises reacting a Bzl-halogen-benzanthrone selenides,

with selenium to produce a benzanthrone-hydrogen-selenide.

9. The process of preparing a benzanthronehydrogen-selenide, which comprises reacting a Bzl-halogen-benzanthrone with selenium under conditions milder than those leading to a dibenzanthronyl selenide.

10. The process of preparing dibenzanthronylselenone, which comprises subjecting dibenzanthronyl-selenide to the action of a mild oxidizing agent.

11. The process of preparing a compound containing a benzanthrone nucleus and also containing selenium, which comprises reacting a Bzlhalogen benzanthrone with selenium to produce a mono-benzanthrone-selenol, and reacting the latter with an etherifying agent to replace the hydrogen atom of the selenol radical by an organic radical of the alkyl or aryl series.

12. In the manufacture of dyestuffs of the isodibenzanthrone type, the process which comprises heating a Bzl, Bzl'-dib-enzanthronyl-selenide with aluminum chloride.

13. Substitution derivatives of Bzl, Bzl'-diben-'- zanthronyl-selenides as may be prepared by subjecting Bzl, Bzl'-dibenzanthronyl selenide to an operation selected from the group consisting of oxidation, nitration, and sulfonation.

14. In the manufacture of a compound containing at least one benzanthrone nucleus and also containing selenium, the step which comprises heating a Bzl-halogen-benzanthrone with selenium in alcoholic medium, in the presence of an acid absorbing agent.

ROBERT FRASER THOMSON. IAN BLOI-IM ANDERSON. SIDNEY THORNLEY. 

